EP0728787B1 - Composition useful for lacquers based on mixtures of emulsions and dispersions of polymer polyols and coatings prepared therefrom - Google Patents

Abstract

A compsn. comprising (i) at least one opt. masked polyisocyanate (I) in the form of an aq. emulsion with an ave. particle size d50 of 0.0-10 micrometers, pref. less than 2 and greater than 0.2 micrometers and (ii) at least one polyhydroxylated polymer (II), esp. a polyol, in the form of an aq. dispersion with an ave. particle size d50 of 10-200 nm, whereby the (II) is present in an amt. of at least = 35 - 0.75 R, pref. at least 40 - 0.75 R, and esp. at least 45 - 0.75 R wt.% or at most 45 - 2 R, pref. at most 40 - 2 R and esp. at most 35 - 2 R wt.%, where R = d50(I)/d50(II).

Description

The present invention relates to mixtures of emulsions with dispersions of polymer. It relates more particularly to the stability of a dispersion of polyol together with an isocyanate emulsion, most often masked.

Such compositions are particularly useful for varnishes and painting, but they can be useful for any application using the properties of isocyanate condensation. They can also be useful in any field in which we have to coexist isocyanate emulsions, in general blocked, with dispersions of insoluble alcohols of grain size different and especially in the formulations for agriculture.

In the remainder of this description, the term dispersion will be used for polymers with hydroxyl functions and in particular polyols, however that will use the expression emulsions for isocyanates, blocked or not.

The use of organic solvents is increasingly criticized by authorities responsible for work safety, because these solvents, or at least some of them are considered toxic or chronotoxic. That's the reason for which we are trying to develop more and more techniques which replace techniques in a solvent medium to overcome the drawbacks related to solvents.

One of the most often used solutions is the use of emulsions or dispersions in water.

To make films of paints or varnishes, two dispersions are mixed, an emulsion containing the isocyanate which can be blocked and a dispersion of polyol.

The mixture of dispersions may also contain pigments and charges is then deposited on a support in the form of a film using classic techniques for using industrial paints. When the preparation contains blocked isocyanates, the whole film plus support is cooked at a temperature sufficient to ensure the unlocking of functions isocyanates and the condensation of these with hydroxyl groups polyol particles.

In the present description, the particle size characteristics often refer to notations of the type d _n where n is a number from 1 to 99, this notation is well known in many technical fields, but is a little more rare in chemistry, also may it be useful to recall its meaning. This notation represents the particle size such that n% (by weight, or more exactly by mass, since the weight is not an amount of matter but a force) of the particles is less than or equal to said size.
In the following description, the polydispersity index will be used, which is defined as I = (d 90 -d 10 ) / D 50

Typically, the ratios of the average sizes (d ₅₀ ) between the isocyanate emulsion and the polyol dispersion are between 2 and 200. Thus the average sizes of the isocyanate emulsions manufactured according to the technique described in the French patent application filed on 03.31.1993 under No. 93 03795 and published under No. 2703358 on 07.10.94, have average sizes between 0.1 and 10 micrometers and more generally between 0.3 and 2 micrometers. The polyol dispersions used in combination with these emulsions have average sizes measured by quasi-elastic light scattering of between 20 and 200 nanometers and more generally between 50 and 150 nanometers.

When mixing dispersions of different sizes, which is generally the case, so as to obtain molar ratios between the NCO and OH groups between 0.3 to 10 and more preferably between 0.8 and 1.5, instability of the mixtures of the two dispersions is observed.

For example, this instability results in a macroscopic separation fast, generally in a few minutes, to give a phase on the one hand fluid and on the other hand a very viscous phase.

It follows not only an impossibility of preserving (storing) these mixtures, but also an extreme difficulty in applying this mixture on the surface which it is desired to cover according to the usual techniques for applying paints and varnishes. If we make sure to apply these unstable mixtures on a support, such as on a glass or metal plate, the resulting film is not transparent but appears opaque and heterogeneous and therefore not suitable.
To solve this problem, the European application published under No. 0 358 979 proposes using a polyol in which the isocyanate is emulsified; the same applicant's subsequent application No. 0 557 844 proposes a similar solution using, where appropriate, thickeners.
These problems are particularly acute in the case of isocyanates, masked or not, when they are mixed with non-soluble polyols dispersed in water.

Thus, one of the aims of the present invention is to provide a technique which provides stable and fluid mixtures of an isocyanate emulsion with polyol dispersions which are stable "per se", in particular without it should be added additional additive or neutralizer for example for adjust a pH.

Another object of the present invention is to provide compositions comprising an emulsion of masked isocyanates and a dispersion of polyols which are physically stable for at least one month.

The other object of the invention is to obtain, from these stable and fluid mixtures of this emulsion with a polyol dispersion, films having good gloss, transparency and resistance to solvents.

• - au moins un polyisocyanate masqué ou non sous la forme d'une émulsion aqueuse dont la taille moyenne est comprise entre 0,1 et 10 micromètres et de préférence inférieure à 2 et supérieure à 0,2 micromètre.
• - au moins un polymère polyhydroxylé, avantageusement un polyol, sous forme d'une dispersion aqueuse dont la taille moyenne est comprise entre 10 et 200 nanomètres. La quantité en polymère(s) polyhydroxylé(s) du mélange étant choisie de manière à répondre à l'une des deux contraintes suivantes :
  • la teneur en polymère(s) polyhydroxylé(s) exprimée en pour cent massique est au moins égale à 35 - 0,75 R, avantageusement au moins égale à 40 - 0,75 R, de préférence à 45 - 0,75 R ;
  • la teneur en polymère(s) polyhydroxylé(s) exprimée en pour cent massique est au plus égale à 45 - 2 R, avantageusement au plus égale à 40 - 2 R, de préférence à 35 - 2 R ;
  avec R égal au rapport entre la taille moyenne (d₅₀) de l'émulsion et celle de la dispersion de polymère polyhydroxylé, avantageusement de polyol, et avec la condition que R soit au moins égal à 2.

Le rapport (R) entre les tailles moyennes des particules élémentaires (d₅₀) de l'émulsion et celle de la dispersion de polyol étant au moins égal à 2 plus souvent est compris entre 8 et 40 et plus généralement autour de 30.
Il est très souhaitable que l'émulsion et /ou la dispersion soit aussi peu dispersée que possible.
Ainsi pour les polymères polyhydroxylés, l'indice de polydispersité (défini comme I = (d₉₀-d₁₀)/d₅₀) est au plus égal à 2 avantageusement égal à 1, les meilleurs résultats étant obtenus pour des valeurs de 0,2 à 0,1 voire moins. These aims are achieved by means of a composition comprising:

• - At least one polyisocyanate masked or not in the form of an aqueous emulsion whose average size is between 0.1 and 10 micrometers and preferably less than 2 and more than 0.2 micrometer.
• - At least one polyhydroxylated polymer, advantageously a polyol, in the form of an aqueous dispersion whose average size is between 10 and 200 nanometers. The quantity of polyhydroxylated polymer (s) of the mixture being chosen so as to meet one of the following two constraints:
  • the content of polyhydroxylated polymer (s) expressed in mass percent is at least equal to 35 - 0.75 R, advantageously at least equal to 40 - 0.75 R, preferably 45 - 0.75 R;
  • the content of polyhydroxylated polymer (s) expressed in percent by mass is at most equal to 45 - 2 R, advantageously at most equal to 40 - 2 R, preferably 35 - 2 R;
  with R equal to the ratio between the average size (d ₅₀ ) of the emulsion and that of the dispersion of polyhydroxylated polymer, advantageously of polyol, and with the condition that R is at least equal to 2.

The ratio (R) between the average sizes of the elementary particles (d ₅₀ ) of the emulsion and that of the polyol dispersion being at least equal to 2 more often is between 8 and 40 and more generally around 30.
It is very desirable that the emulsion and / or dispersion be as little dispersed as possible.
Thus for polyhydroxylated polymers, the polydispersity index (defined as I = (d ₉₀ -d ₁₀ ) / d ₅₀ ) is at most equal to 2 advantageously equal to 1, the best results being obtained for values of 0.2 0.1 or less.

Thus for the polyisocyanates masked or not the polydispersity index defined as (d ₉₀ -d ₁₀ ) / d ₅₀ is at most equal to 2 advantageously equal to 1. The best results being obtained for values of 0.9 to 0, 8 or less.

• la teneur en polymère polyhydroxylé, avantageusement en polyol, exprimée en pourcent massique est au moins égale à 35 - 0,75R, avantageusement au moins égale à 40 - 0,75R, de préférence à 45 - 0,75R ;
• la teneur en polymère polyhydroxylé, avantageusement en polyol, exprimée en pourcent massique est au plus égale à 45-2R, avantageusement au plus égale à 40-2R, de préférence à 35- 2R

avec R égal au rapport entre la taille moyenne (d₅₀) de l'émulsion et celle de la dispersion de polymère polyhydroxylé, avantageusement de polyol.
En d'autre terme R = (d₅₀ de l'émulsion)/(d₅₀ de la dispersion).The formulation zones depend on the ratio R of the average sizes (d ₅₀ ) between the isocyanate emulsion and those of the dispersion of polyhydroxylated polymer (s), advantageously of polyols.
R is equal to the average size of the emulsion over the average size of the dispersion of polyhydroxylated polymer, advantageously of polyol.
According to the invention, the quantity of polyhydroxylated polymer, advantageously polyol, of the mixture is chosen so as to meet one of the following two constraints:

• the content of polyhydroxylated polymer, advantageously of polyol, expressed in percent by mass is at least equal to 35 - 0.75R, advantageously at least equal to 40 - 0.75R, preferably to 45 - 0.75R;
• the content of polyhydroxylated polymer, advantageously of polyol, expressed in percent by mass is at most equal to 45-2R, advantageously at most equal to 40-2R, preferably at 35-2R

with R equal to the ratio between the average size (d ₅₀ ) of the emulsion and that of the dispersion of polyhydroxylated polymer, advantageously of polyol.
In other words R = (d ₅₀ of the emulsion) / (d ₅₀ of the dispersion).

Thus, when R is between 2 and 10, it is the constraint that the polyol content expressed in percent by mass is at least equal to 35-0.75R, advantageously at least equal to 40-0.75R, preferably at 45-0.75R, which gives the most significant area of existence.
For R between 10 and 15, it is possible to find viable solutions in one or the other field defined by the inequalities above.
For R greater than 15, solutions to the problems posed can hardly be found except in the field defined by the condition that the polyol content expressed in percent by mass is at most equal to 45-2R, advantageously at most equal to 40- 2R, preferably 35-2R.
Thus in the domain where R is between 10 and 15, two stable zones of existence coexist.
The ratio between the number of hydroxyl functions and the number of isocyanate functions, masked or not, can vary very widely as has been indicated above.

The ratios lower than the stoichiometry are favorable to plasticity, while that ratios higher than the stoichiometry lead to coatings of high hardness. It is rare that we have reports deviating from the range from 0.5 to 2.
However, in most cases and for the most common uses, in order to obtain satisfactory varnish or paint films, it is preferable that the quantity, expressed in equivalent, of reactive blocked isocyanates is substantially equal to that of free and reactive alcohol functions, expressed in equivalent, that is to say respond to stoichiometry. As an indication, one can indicate that there is a tolerance of more or less 20% compared to the stoichiometry, but it is preferable to use only a tolerance of more or less 10 or 20%.
Isocyanate emulsions are advantageously made according to the technique described in the French patent application published under No. 2703358 on 07.10.94, filed on 31.03.1993 under No. 93 03795 and entitled: "Process for the preparation of aqueous emulsions advantageously masked oils and / or gums and / or (poly) isocyanate resins and emulsions obtained ".

With regard to the additional elements of a composition according to the present invention, it is possible that it further comprises at least one catalyst for the release of masked isocyanates, and in particular of catalysts, latent or not, based on tin. It can be noted that these catalysts can be found either within the polyol phase or within the phase masked isocyanate, either in dispersed form within the aqueous phase keep on going. They can finally be dissolved in the aqueous phase.

The polyol dispersions which can be used for the invention are the conventional products used in the paint and varnish industry. They are most often (co) polymers) produced in emulsion according to the conventional methods of radical or bulk polymerization.

• RHOPLEX® AC-1024 (confère la notice technique édité en 1984) ;
• JONCRYL® 8300 (confère la notice technique CJ8300e/B2) ;
• SANCURE® WATER BORNE URETHANE 815 (confère la notice technique révisée le 01/02/92 et imprimée le 04/01/94) ;
• SYNTHACRYL® VWS 1505( confère la notice technique éditée en septembre 1991).

By way of examples, or rather paradigms, mention may be made of the following commercial polyester or acrylic resins, the list not being exhaustive:

• RHOPLEX® AC-1024 (gives the technical manual published in 1984);
• JONCRYL® 8300 (provides technical manual CJ8300e / B2);
• SANCURE® WATER BORNE URETHANE 815 (gives the technical notice revised on 02/01/92 and printed on 04/01/94);
• SYNTHACRYL® VWS 1505 (gives the technical manual published in September 1991).

These products are in the form of aqueous dispersions (or emulsions) with dry extracts between 20 and 60%. Polyols are characterized by their rate of hydroxyl groups which are given by the manufacturer are assayed analytically.

In the case of paints, any known pigment may be added, to provided that it is inert with respect to the constituents of the composition.

Although it is possible according to the present invention to use non-isocyanates masked, and as these are not very stable in water, the isocyanates preferred are those which are masked in particular by the masking agents in themselves known such as phenols, ketone oximes and in particular that of methyl ethyl ketone, the various pyrazoles.

The preferred isocyanates are those in which the nitrogen of at least one of the isocyanate functions is attached to a sp ³ hybridization carbon advantageously carrying one, and preferably two, hydrogen atom (s). Isocyanates, all of whose functions have this characteristic (with possibly its preferred options), are highly appreciated.

Mention may in particular be made of isocyanates, masked or not, which have a or several isocyanuric rings and / or at least one of the functionalities of biuret or dimer type.

It is preferable that isocyanates having both characteristics specified above, i.e. oligomerism and aliphatic character on at least one of the isocyanate functions.

Advantageously, the water content of said compositions is at least equal to a third of the mass of the composition advantageously at least 2/5.

The preferred polyols are in the form of an aqueous dispersion, they have a average size less than 200 nanometers which presents a greater formulation latitude in combination with isocyanate emulsions. We prefers aqueous dispersions with a low content of compounds soluble in water such as alcohols and amines which can lead to the coalescence of the isocyanate emulsion. It is therefore very desirable that the cumulative content of various alcohols and amines is less than those which induce a coalescence of the isocyanate emulsion.

The present invention also relates to the coatings obtained from the compositions according to the present invention. These coatings can be obtained by crosslinking, in particular by baking at a temperature close to that corresponding to the release of the masked isocyanates optionally in the presence of one or more catalysts.
The following nonlimiting examples illustrate the invention.

Example 1

TOLONATE D2® is a mixture of isocyanuric cycle oligomers essentially trimer masked by the methyl ethyl ketone oxime

JONCRYL® 8300 is an acrylic dispersion with an average diameter of 75 nm measured by quasi-elastic light scattering. The isocyanate is an emulsion of TOLONATE® D2 with an average diameter equal to 1.14 µm measured using a SYMPATEC® granulometer. The ratio of sizes R is equal to 15.2. The mixture containing 36.4% by weight of JONCRYL® and 10.7% by weight of TOLONATE®, which corresponds to a molar ratio [NCO] / [OH] of 1.05, is fluid and stable.
The 100 μm films are drawn on glass plates using a TOUZARD ET MATIGNON automatic applicator, reference ASTM 823, method D. After baking at 150 ° C. for 20 minutes, a transparent 30 μm film is obtained. The PERSOZ hardness of the film is 208. The gloss measured on an ERICKSEN contrast card at an angle of 20 ° is 61.4 and 87.2 at an angle of 60 °. In addition, the film obtained has good resistance to methyl ethyl ketone solvents and to acetone.
The JONCRYL® / TOLONATE® mixture of 6% / 1.9% which corresponds to an NCO / OH ratio of 1.05 gives rise to a macroscopic phase separation and the film obtained is heterogeneous and cloudy.

Example 2

SYNTHACRYL® VSW 1505 is a polyol dispersion with an average diameter of 65 nm measured by quasi-elastic light scattering. The isocyanate is the same as that used previously. The size ratio R is 17.5. The mixture containing 28.6% by weight of SYNTHACRYL® VSW 1505 and 19.9% by weight of TOLONATE®, which corresponds to a molar ratio [NCO] / [OH] of 2.62 is fluid and stable.
The 100 μm films are drawn on glass plates using a TOUZARD ET MATIGNON automatic applicator, reference ASTM 823, method D. After baking at 150 ° C. for 20 minutes, a film is obtained which has good resistance to methyl ethyl ketone and acetone solvents.
The SYNTHACRYL® VSW 1505 / TOLONATE® mixture of 15% / 10% which corresponds to an NCO / OH ratio of 2.52 gives rise to a macroscopic phase separation between a fluid phase and a flocculated mixture.

Example 3

RHOPLEX® AC 1024 is a polyol dispersion with an average diameter of 135 nm measured by quasi-elastic light scattering. The isocyanate is the same as that used previously. The size ratio R is 8.4. The mixture containing 15% by weight of RHOPLEX® AC 1024 and 10% by weight of TOLONATE®, which corresponds to a molar ratio [NCO] / [OH] of 4.8, is fluid and stable.
The 100 μm films are drawn on glass plates using a TOUZARD ET MATIGNON automatic applicator, reference ASTM 823, method D. After baking at 150 ° C. for 20 minutes, a film is obtained which has good resistance to methyl ethyl ketone and acetone solvents.
The RHOPLEX® AC 1024 / TOLONATE® mixture of 40% / 10% corresponds to an NCO / OH ratio of 1.8. This mixture gives rise to a macroscopic phase separation between a fluid phase and a flocculated mixture.

Example 4

SANCURE 815 is a polyol dispersion with an average diameter of 35 nm measured by quasi-elastic light scattering. The isocyanate is the same as that used previously. The ratio of sizes R is equal to 32.5. The mixture containing 20% by weight of SANCURE and 10% by weight of TOLONATE® is fluid and stable.
The SANCURE / TOLONATE® mixture of 8% / 8% which corresponds gives rise to a macroscopic phase separation between a fluid phase and a flocculated mixture.

Claims (9)

1. Composition comprising:

   at least one masked or unmasked polyisocyanate in the form of an aqueous emulsion whose mean size is between 0.1 and 10 micrometres and preferably smaller than 2 and larger than 0.2 micrometres;

   at least one polyhydroxylated polymer, advantageously a polyol, in the form of an aqueous dispersion whose mean size is between 10 and 200 nanometres;

   characterized in that the quantity of polyhydroxylated polymer(s) in the mixture is chosen so as to meet either of the following two constraints:

   the content of polyhydroxylated polymer(s) expressed in mass per cent, is at least equal to 35 - 0.75R, advantageously at least equal to 40 - 0.75R, preferably to 45 - 0.75R;

   the content of polyhydroxylated polymer(s), expressed in mass per cent, is at most equal to 45 - 2R, advantageously at most equal to 40 - 2R, preferably to 35 - 2R;

   with R equal to the ratio of the mean size (d₅₀) of the emulsion to that of the dispersion of polyhydroxylated polymer, advantageously of polyol, and with the condition that R is at least equal to 2.
2. Composition according to Claim 1, characterized in that the said polyisocyanate(s), masked or otherwise, has(have) a polydispersity index, defined as (d₉₀-d₁₀)/d₅₀, at most equal to 2, advantageously equal to 1.
3. Composition according to Claims 1 and 2, characterized in that the said polyhydroxylated polymer(s) has(have) a polydispersity index, defined as I = (d₉₀-d₁₀)/d₅₀, at most equal to 2, advantageously equal to 1.
4. Composition according to Claims 1 to 3, characterized in that it additionally comprises at least one catalyst of release of the masked isocyanates, and especially tin-based catalysts, latent or otherwise.
5. Composition according to Claims 1 to 4, characterized in that the water content of the said composition is at least equal to one third of the mass of the composition, advantageously to at least 2/5.
6. Composition according to Claims 1 to 5, characterized in that the said polyisocyanate(s) has(have) one or more isocyanuric rings and/or at least one of the functionalities of the biuret or dimer type.
7. Composition according to Claims 1 to 6, characterized in that the said polyisocyanate is chosen from those in which the nitrogen of at least one of the isocyanate functional groups is attached to a carbon with sp³ hybridization advantageously carrying one, and preferably two, hydrogen atom(s).
8. Composition according to Claims 1 to 7, characterized in that the said polyisocyanate is chosen from those which are masked especially by masking agents which are themselves known, such as phenols, ketone oximes and especially methyl ethyl ketone oxime, and the various pyrazoles.
9. Coating characterized in that it is capable of being obtained by crosslinking from the compositions according to Claims 1 to 8.